Anthraquinone derivatives



Patented Aug. 21 1945 UNITED 7 STATES PATENT. OFFICE Y t ANIHRAQUIZZSSZZSSERWAMS gott, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a cor-.

. porationof Great Britain No Drawing. Application June 13, 1942, Serial No.446,9 28. In Great Britain July '7, 1941 1 2 claim (01. 2 -379) This invention relates to the manufacture and no, chloro, bromo and nitro substituents. The alkoxy, alkylamino and hydroxyalkylamino sub- 1 stituents, when present, are such as do not contain more than carbon atoms. Similarly the arylamino substituents consist of anilino, toluidino andxylidino substituents, and the aryloxy swbstituents of phenoxy and tolyloxy ones.

According to the invention we make the. said new derivatives by interacting an alkoxyalkoxyalkylamine or an alkoxyalkoxyalkoxyalkylamine having 5-10 carbon atoms with an anthraquinone derivative which carries one or more replaceable substituents, as further defined below, directly attached to the anthraquinone nucleus, and/or one or more chlorine or bromine atoms attached to the .anthraquinone nucleus through a CO group, and which may also carry one or more hydroxyalkylamino orarylamino substituents as defined above. i i

The said replaceable substituents are hydroxy, alkoxy, aryloxy, amino, alkylamino, chloro, bromo, nitro and sulphosubstituents in a posi tions in the anthraquinone nucleus.

According to a modification ofthe invention, when the replaceable substituents are hydroxy, amino or alkylamino groups, theanthr'aquinone derivatives are interacted in the .form ofitheir leucq derivatives, or partlyin the form of their leuco derivatives, and the resulting products,

which are in the form of leuco derivatives or partly in this form, then oxidised to the ordinary quinone form.

Also according to products of the invention as definedabove, when these still carry one or more replaceable substituents, with ammonia, alkylamines or hydroxyah.

the invention We interact the dimethylaminoanthraquinone, 1:4 diaminoanthraquinone and 1 z 4 :5 8-tetrahydroxyanthraquinone, and their leuco derivatives, 1-amino-4- hydroxy-anthraquinone, 1 l-dibromoanthraquinone, 4-nitro-L-methoxy-anthraquinone, .e-nitrol-aminoanthraquinone-.Z-carboxyl chloride and 1- nitro-anthraquinone-2-carboxyl chloride;

The preparation of 4-nitro-1-aminoanthraquinone-Z-canboxyl chlorideisdescri-bed in Specification No. 350,928, p. 3, lines 101-121. l-Nitroanthraquinone-2-carboxyl. chloride is prepared by] heating 1-nitroanthraquinone Z-caiboxylic, acid with thionyl, chloride in nitrobenzene, and 4-nitro-I-methQXyanthraQiiinOne is prepared by nitration of l-methoxy anthraquinone. I

The alkoxyalkoxyalkylamines, and the alkoxyalkoxyalkoxyalkylamines may be obtained by Var- 1 1011s methods. fl-Amino-d-methoxydiethfl ether kylamines containing not more than 5 carbon atoms, or with arylamines. U

vAlso accordingtothe invention we reduce the products of the invention when obtained accord ing to the first defined process and also containing an unreplaced nitr substituent, so, as to obtain the corresponding. amine.

wAs particular examples ofanthraquinone dea rivatives. containing replaceable substituents as defined there may be mentioned quinizarin, 1:4-

persing agents.

and the corresponding ethoxy, butoxy and other alkoxy compounds may be obtained ,by, heating the corresponding 5 chloro-,cl-alkoxydiethyl others (prepared by interacting pp dichlorodiethyl ether and sodium alkoxides, as described..105

Cretcher & Pittenger, J. Amer. Chem. Soc; 1925,-

47, 164) with aqueous ammonia 1101100? 0. Aminoethyl-p-methoxyisopropyl ether may be prepared by interacting methyl p-hydroxypropyl ether, formaldehyde and hydrochloric acid, treatment of the product withcuprous cyanide, andcatalytiohydrogenation of the ,Bj-xtrethoxyisopropoxyacetonitrile f thus obtained. f li-Amino-ethyl pH-dialkoxyisopropfl.ethers may be obtained in a similar mannenfrom glycerol 1 3-dia 1ky1 ethers.

The newderivatives are useful as intermediates for dyestuffs and/or as dyestuffs foracetate rayon. As acetate rayon dyestuffs they are, in

general, characterised by good penetrating PI'OD-r erties",.high affinity .1 and g ood general fastness properties. They possess some solubility inwater and their dyeing and-printing properties may be improved Where necessary by milling with dis- The invention also includes the useoi the new derivatives for colouring acetate rayon. 45

The following examples in which parts are by. weight illustrate but do notlimit the invention.

Examp lel 30 parts of [3-amino-fi--methoxydiethyl ether,

10 parts of (NI-I2.CH2.CH2.0.CH2.CH2.0.CH3) quinizarin, 10 parts of leucoquinizarin, and parts of iso-butanol are boiled together underreflux" for 15. hours. 1 part. of pyridine is, then I, added and a stream of air is passed. through the boiling solution to oxidise the leuco compound.

Example 2 I 16.5 parts of diethyleneglycol-methyl-fi-aminoethyl ether,

obtainable by condensing ethyleneglycol monomethyl ether with fi,6'-d.ichlorodiethyl ether and reacting the product with ammonia, 4 parts of quinizarin, 4 parts of leucoquinizarin and 30 parts of isobutan-ol are boiled under reflux for 15 hours, and then oxidised as in Example 1. The product, isolated by evaporation'to dryness, is readily soluble in water and dyes acetate rayon in bright blue shades.

Example 3 150 parts of diethyleneglycol methyl-fl-aminoethyl ether, 100 parts of l-chloroanthraquinone, 35 parts of potassium carbonate, 1 part of copper acetate and 300'parts of isobutanol are boiled together under reflux for 12 hours. After cooling, the dyestufi, which separates out in the form of red crystals, is isolated by filtration and washed with isopropanol and water. It consists essentially of 1-( 3"-methoxy pf-ethoxy-,8-ethoxy ethylamino) anthraquinone and dyes acetate rayon in clear yellowish-red shades.

A dyestuif very similar in shade and properties is obtained if the diethyleneglycol methyl [3- aminoethyl ether is replaced b the equivalent amountof fl-am'inoethyl ,Bpdimethoxyisopropyl ether (NH2CH2.CH2OCH(CH2OCH3)2) Example 4 100 parts of 4-bromo-l-methylaminoanthraquinone, 120 parts of diethyleneglycol methyl 5- aminoethyl ether, 27 parts of potassium carbonate, 1 part of copper acetate and 120 parts of nitrobenzene are stirred together at 135-140 C. for 12 hours. The mixture is then diluted with 400'parts of isopropanol and cooled to 5 C.; the precipitated dyestuff is filtered off and washed with iso-propanol and cold water. It is readily dispersed in water when mixed with suitable dispersing agents, and dyes acetate silk in reddish blue shades.

Example 5 8 parts of p-amino-p'-methoxydiethyl ether, 10 parts of quinizarin, 2 parts of leucoquinizarin and 40 parts of isobutanolare boiled together under reflux for 12 hours. After cooling the dyestufi separates in the form of violet needles and is isolated by filtration. It consists mainly of 4-1hydroxy 1 e methoxy p ethoxyethylaminoanthraquinone, and dyes acetate silk in clear violet shades.

- Example 6 4 parts of sodium anthraquinone-l-sulphonate, 1 part of sodium m-nitrobenzenesulphonate, 8 parts of diethyleneglycol methyl-,o-aminoethyl ether and 20 parts of water are stirred and heated together in an autoclave at 160 C. for 6 hours. The mixture is cooled and the red condensation product separated by filtration. It is identical with the product of Example 3.

Example 7 8 parts of 1 nitroanthraquinone 21- carboxyl chloride are added to a solution of 16 parts of p-amino-B'-methoxydiethyl ether in 30 parts of isopropanol, and the mixture stirred and heated at C. for 2 hours. After cooling the mixture is poured into 500 parts of water and allowed to stand for some hours. The product, which separates in the form of small red crystals and is isolated by filtration, consists essentially of the dyestuff corresponding with the formula:

' o NHCHz.CHzOOHz.OHz.OCHa

-O 0 .NHCH2.CH2O CHz.CH2O CH3 It is somewhat soluble in water; and after dispersion gives a product which dissolvesin water to form clear solutions, from which acetate rayon is dyed in'bright red shades of good fastness properties.

Example 8 24 parts of ,e-aminmp'-methoxydiethyl ether, 20 parts of leuco- 1': 4 5 8-tetrahydroxyanthraquinone, 5 parts of boric acid and 75 parts of isobutanol are boiledtogether under reflux for 12 hours. After oxidation and isolation as nescribed in Example 1, the dyestufi is obtained in the form of bronze plates, and when suitably dispersed it dyes acetate rayon in brilliant bluegreen shades.

Example 9 50 parts of finelypowclered lnitroanthraquinone-2-carboxyl chloride are added to a solution of 42 parts of {3-arnino-fi methoxydiethyl ether in 1000 parts of water, and stirred for several Example 10 I v 10 parts of finely powdered 4-nitro 1-aminoanthraquinone- 2-carboxyl chloride ar'ea'ddedto a solution of 10 parts of -13-amino-p' methoxydiethyl ether in parts of water. The mixture is stirred in the cold for several hours and-the condensation product consisting essentially fof the ,5emethoxy cethoxyethylamide of 4-nitro- 1-aminoanthraquinone-2-carboxylic acid, is separated by filtration. It isreduced to the corresponding diamino'compound by heating at 50 C. with a solution of 17 parts of crystalline 'sodium sulphide in 100 parts of water. After cooling, filtering and washing with water the dyestuif is isolated as a violet'powder. When mixed with suitable dispersing agents it 'dissolvesfin gether under reflux for 6 hours. oxidised and isolated as described in Example 1, is obtained in the form of blue needles, identical 1 with the product of Example'l.

' water to give clear solutions from which acetate silk is dyed in bright blue-violet shades of excellent fastness properties.

Example 11 8 parts of leuco-l: l-dimethylaminoanthraquinone, 16 parts of p-amino-a-methoxydiethyl ether and parts of isobutanol are boiled to- The dyestufi,

The equivalentamount of leuco-lz i-diaminoanthraquinone may be used in place of the dimethyl derivative.

Example 12 10 parts of finely. divided 4-nitro-,1-methcxyanthraquinone, 6.5 parts or fi-amino-fi' methoxydiethyl ether and 50 parts of ethyleneglycol monoethyl ether are stirred together at 80 C. for 18 The mixture isthen cooled and poured.

hours. into a large volumeof water, and the precipitate is filtered off and dried. The crude product is extracted thoroughly with boiling ethanol and, on cooling, the extract deposits red needles, consisting wholly or mainly of 4-nitro-1-fl-methoxyfl-ethoxyethylaminoanthraqulnone. On warming with sodium sulphide solution this is reduced to the corresponding amino compound, which dyes acetate rayon in bright violet shades.

Example 13 '35 parts of finelypowdered 4-bromo-1-aminoanthraquinone-2-carboxyl chloride (prepared according to the method of British Specification No. 492,291) are added to a solution of parts of ,B-amino-fl'-methoxydiethyl ether in 350 parts of water and stirred for several hours. The condensation product, consisting mainly of the 5'- methoxy-,8-ethoxyethylamide of 4-bromo-1-amincanthraquinone-2-carboxylic acid, is separated by filtration and washed with water.

A mixture of 100 parts of this amide with 50 parts of potassium acetate, 1 part of copper acetate and 200 parts of aniline is stirred and heated at 120-125? C. for 16 hours. 'The mixture is then diluted with twice its volume of ethanol and poured into a large volume of dilute hydrochloric acid. After standing for some timethe condensation product solidifies and is isolated by iiitration. It consists essentiallyof the p-methoxy- ,B-ethoxyethylamide of l-aminol-anilinoanthraquinone-Z-carboxylic acid, and, when suitably dispersed, dyes acetate rayon in blue shades of good fastness properties.

Example 14 A mixture of parts of the ,3-methoxy-pethoxyethylamide of 4-bromo-1-'aminoanthraquinone-2-carboxylic acid (prepared as described in Example 13), 50- parts of potassium acetate, 1 part of copper acetate and 200 parts of p-anisidine is stirred andheated at -125 C. until a bright blue solution results. The mixture is then cooled, diluted with 1000 parts of ethyl alcohol and allowed to stand until the crystallisation of the condensation product is complete. After filtration and recrystallisation fromethanol the product consisting essentially of the ,8-meth oxy-[B-ethoxyethylamide of l-aminol-p-anisidinoanthraquinone-Z-carboxylic acid, is obtained in the form of dark blue needles with a metallic lustre. When suitably dispersed it dyes acetate rayon in bright greenish blue shades.

Asmany widely different embodiments of this. invention may be made without departing from 'the spirit and scope thereof,.it is to be understood that we do not limit ourselves to the spe-- cii-lc embodiments thereof except as defined in the appended claims. 1

Weclaim: 1 1. The anthraquinone compounds of the formula: a

o NHR wherein X stands for a substituent of the class consisting of -NHCH3 and NHR where in each case R stands for an alkoxy substituted alkyl radical of the group consisting of alkoxy-alkoxyalkyland alkoxy-alkoxy-alkoxy-alkyl radicals in which the alkoXy substituted alkyl radicals contain from 5 to 10 carbon atoms.

2. 1,4-di- (p'-methoxy-p-ethoxyethylamino) anthraquinone.

. GERARD DUNSTAN BUCKLEY.

HENRY ALFRED PIGGOTT. 

